CN109912451B - Preparation and application of 4-hydroxybenzophenone hydrazone-salicylaldehyde Schiff base - Google Patents
Preparation and application of 4-hydroxybenzophenone hydrazone-salicylaldehyde Schiff base Download PDFInfo
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- CN109912451B CN109912451B CN201910274655.0A CN201910274655A CN109912451B CN 109912451 B CN109912451 B CN 109912451B CN 201910274655 A CN201910274655 A CN 201910274655A CN 109912451 B CN109912451 B CN 109912451B
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- 238000002360 preparation method Methods 0.000 title abstract description 4
- 239000002262 Schiff base Substances 0.000 title description 11
- -1 4-hydroxybenzophenone hydrazone-salicylaldehyde Schiff base Chemical class 0.000 title description 4
- 239000013078 crystal Substances 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- AIUATHLWVBCHAE-KIRJRVOOSA-N 2-[(E)-[(Z)-[(4-hydroxyphenyl)-phenylmethylidene]hydrazinylidene]methyl]phenol Chemical compound OC1=CC=C(C=C1)\C(\C1=CC=CC=C1)=N/N=C/C1=C(C=CC=C1)O AIUATHLWVBCHAE-KIRJRVOOSA-N 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims abstract description 3
- 230000008018 melting Effects 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- MBBAQOHSSWERBC-UHFFFAOYSA-N 4-(C-phenylcarbonohydrazonoyl)phenol Chemical compound OC1=CC=C(C=C1)C(C1=CC=CC=C1)=NN MBBAQOHSSWERBC-UHFFFAOYSA-N 0.000 claims description 7
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 206010028980 Neoplasm Diseases 0.000 claims description 4
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- 201000007270 liver cancer Diseases 0.000 claims description 3
- 208000014018 liver neoplasm Diseases 0.000 claims description 3
- 201000005202 lung cancer Diseases 0.000 claims description 3
- 208000020816 lung neoplasm Diseases 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
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- 208000026310 Breast neoplasm Diseases 0.000 claims description 2
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- 239000003960 organic solvent Substances 0.000 description 8
- 150000004753 Schiff bases Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
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- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
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- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
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- 229910021645 metal ion Inorganic materials 0.000 description 2
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- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000002965 ELISA Methods 0.000 description 1
- 108010019160 Pancreatin Proteins 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
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- 229910052751 metal Chemical class 0.000 description 1
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- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention relates to a structure, a preparation method and partial properties of a compound. The compound is orange blocky crystal in appearance, and the melting point of the compound is as follows: 146.7-148.1 deg.C, molecular formula C20H16N2O2The chemical name is: 2- ((E) - ((((Z) - (4-hydroxyphenyl) (phenyl) methylene) hydrazono) methyl) phenol; the structure of the compound is detailed in the specification, and the compound has certain fluorescence property and anticancer activity.
Description
Technical Field
The invention relates to the fields of organic synthesis, optical materials, pharmaceutical chemistry and the like, and a target product is synthesized in one step by using a simpler method.
Background
At present, with the continuous progress of modern science and technology, people have more and more researches on fluorescence and the fluorescence properties of the fluorescence are also more and more deeply researched. The fluorescent substance is widely applied to the fields of dyes, organic pigments, optical brighteners, photo-oxidizers, coatings, chemical and biochemical marking analysis, solar collectors, anti-counterfeiting marks, medicine tracing, lasers and the like. The organic fluorescent material is mainly used in the current popular technology, such as fluorescent probes, fluorescence analysis and the like, and is an indispensable material for optical electronic devices, DNA diagnosis, photochemical sensors, laser dyes and organic electroluminescent devices.
Schiff bases are mainly organic compounds containing imine or azomethine characteristic groups (-RC ═ N-), and are usually formed by condensation of amines and active carbonyl groups. Schiff base compounds and metal complexes thereof have important application in the fields of medicine and pharmacology, catalysis, analytical chemistry, corrosion and photochromism. In the medical field, Schiff base has biological activities of bacteriostasis, sterilization, anti-tumor and antivirus; in the field of catalysis, complexes of cobalt, nickel and palladium of schiff bases have been used as catalysts; in the field of analytical chemistry, Schiff bases are used as good ligands and can be used for identifying and identifying metal ions and quantitatively analyzing the content of the metal ions; in the corrosion field, certain aromatic schiff bases are often used as corrosion inhibitors for copper; certain schiff bases containing characteristic groups also have unique applications in the field of photochromism.
Disclosure of Invention
The invention relates to a compound which can be used as fluorescent material and anticancer drug, wherein the compound is orange bulk crystal with melting point: 146.7-148.1 deg.C, molecular formula C20H16N2O2The chemical name is: 2- ((E) - (((Z) - (4-hydroxyphenyl) (phenyl) methylene) hydrazono) methyl) phenol, having the structure:
1. and (3) structural identification:
elemental analysis showed that this compound has the formula C20H16N2O2(ii) a The analysis of the single crystal structure shows that the crystal belongs to a monoclinic system, the space group is P21/c,
β＝92.096(5)°，
z is 4, related to1The HNMR spectrum is shown in figure 1; FIG. 2 and FIG. 3 are a thermal ellipsoid crystal structure diagram and a crystal structure stacking diagram of the compound, respectively;
2. a synthetic method.
The synthesis method is characterized in that: the method takes 4-hydroxybenzophenone hydrazone and o-hydroxybenzaldehyde as raw materials, and completes the steps in a proper organic solvent in one step, and comprises the following steps:
1) dissolving 4-hydroxybenzophenone hydrazone in a proper organic solvent, adding o-hydroxybenzaldehyde according to a certain substance quantity ratio, and stirring or grinding at a certain temperature for reacting for several hours to complete the preparation.
2) Filtering, and naturally volatilizing the filtrate to separate out orange blocky crystals which are target products; if solid phase reaction is adopted, the target product crystal can be obtained by recrystallization with proper organic solvent after the reaction is finished.
The method II can also be adopted for synthesis, and is characterized in that: 4-hydroxybenzophenone hydrazone and o-hydroxybenzaldehyde are taken as raw materials and are finished in one step in a proper organic solvent. The method comprises the following steps:
1) dissolving o-hydroxybenzaldehyde in proper organic solvent, adding 4-hydroxybenzophenone hydrazone according to a certain substance amount ratio, and stirring or grinding at a certain temperature for reaction for several hours.
2) Filtering, and naturally volatilizing the filtrate to separate out orange blocky crystals which are target products; if solid phase reaction is adopted, the target product crystal can be obtained by recrystallization with proper organic solvent after the reaction is finished.
The two above processes differ in the order of addition of the reactants, but the molar ratio of the reactants is between 4:1 and 1: 4.
The organic solvent (solvent for reaction or solvent for recrystallization) in the above two methods is selected from: methanol, ethanol, acetonitrile, dichloromethane, chloroform, tetrahydrofuran, acetone, etc., and the reaction may be carried out without using an organic solvent, but the raw materials may be reacted directly (solid phase reaction).
Preferably, the reaction temperature is normal temperature or heating reflux, and the reaction method is stirring or grinding.
Preferably, the reaction time is selected from: 1-10 h.
The invention has the beneficial effects that: can synthesize more complex functional molecular materials by simpler steps and reactants.
3. Ultraviolet and fluorescent properties
The compound has three strong absorption peaks near 207.0, 310.0 and 360.0nm, and the ultraviolet spectrum is shown in figure 4; has strong fluorescence emission peak in the range of 500.0-620.0nm, and the fluorescence spectrum is shown in figure 5.
4. In vitro antitumor activity:
a549 lung cancer cells growing in logarithmic phase，4T1Breast cancer cell and Hep G2 liver cancer cell were prepared by digesting the cells with 0.25% pancreatin to give single cells, and preparing into 1.25 × 10 concentration by using 10% fetal calf serum-containing F12K culture solution7One cell/L suspension of single cells, cells were seeded in 96-well plates at 200. mu.L per well (2.5X 10 per well)3Individual cells). Place 96-well cell culture plates in CO2In an incubator at 37 ℃ with 5% CO2Culturing for 48h under the condition.
When the cells in the wells are full (90% full), adding different doses of the Schiff base solution (200 muL/well) according to experimental groups to make the final concentration of the compound to be detected respectively 5 muM, 10 muM, 30 muM, 50 muM and 100 muM, setting 3 multiple wells in each group, and culturing for 96 h.
mu.L of MTT at a concentration of 0.5g/L was added to each well, and the culture was continued for 4 hours to reduce MTT to Formazan (Formazan). After all the supernatants were aspirated, 200. mu.L of DMSO was added to each well, and the mixture was shaken for 15min to dissolve formazan sufficiently, and then absorbance (OD value) at 490nm was measured using an ELISA detector. Then calculated according to the following formula:
percent cell inhibition (control OD value-experimental OD value)/control OD value × 100%
Test results show that the Schiff base can be used for treating A549 lung cancer cells and 4T1IC50 (half inhibition concentration of the drug) of the breast cancer cell and the Hep G2 liver cancer cell is 143.7 mu M, 141.4 mu M and 130.5 mu M respectively, which shows that the compound has certain inhibition effect on the three cancer cells.
Detailed Description
For better understanding of the present invention, the technical solution of the present invention is further illustrated by a specific example below:
example 1
0.21g (about 1.0mmol) of 4-hydroxybenzophenone hydrazone was weighed out and dissolved in 50ml of acetonitrile, the solution was put into a flask, and stirred on a magnetic stirrer heated at a constant temperature, 0.12g (about 1.0mmol) of o-hydroxybenzaldehyde was weighed out and added to the solution, and the reaction was stirred under heating and reflux for 1 hour. The solution gradually turns yellow, after the reaction is finished, the solution is filtered, and the filtrate is kept stand and naturally volatilized. And separating out orange blocky crystals at the bottom of the beaker, namely the target product.
Drawings
FIG. 1 is a drawing of 2- ((E) - ((((Z) - (4-hydroxyphenyl) (phenyl) methylene) hydrazono) methyl) phenol1HNMR spectrogram.
FIG. 2 is a crystal structure diagram of 2- ((E) - ((((Z) - (4-hydroxyphenyl) (phenyl) methylene) hydrazono) methyl) phenol.
FIG. 3 is a graphic representation of the crystal structure of 2- ((E) - ((((Z) - (4-hydroxyphenyl) (phenyl) methylene) hydrazono) methyl) phenol.
FIG. 4 is a UV spectrum of 2- ((E) - ((((Z) - (4-hydroxyphenyl) (phenyl) methylene) hydrazono) methyl) phenol.
FIG. 5 is a fluorescence spectrum of 2- ((E) - ((((Z) - (4-hydroxyphenyl) (phenyl) methylene) hydrazono) methyl) phenol.
Claims (3)
1. A compound which is an orange bulk crystal in appearance and has a melting point: 146.7-148.1 deg.C, molecular formula C20H16N2O2The chemical name is: 2- ((E) - (((Z) - (4-hydroxyphenyl) (phenyl) methylene) hydrazono) methyl) phenol, having the structure:
the crystal belongs to monoclinic system, space group is P21/c,
β＝92.096(5)°，
Z＝4。
2. a method of synthesizing a compound as claimed in claim 1, characterized in that: there are two synthetic methods, liquid phase synthesis or solid phase synthesis:
1) if a liquid phase synthesis method is adopted, dissolving 4-hydroxybenzophenone hydrazone in methanol, ethanol, acetonitrile, dichloromethane, chloroform, tetrahydrofuran or acetone completely, adding o-hydroxybenzaldehyde according to the mass ratio of 4: 1-1: 4, stirring and reacting for 1-10 hours at normal temperature or at the reflux temperature after heating, filtering, and obtaining orange blocky crystals which are separated out after natural volatilization of the filtrate, namely the target product;
2) if a solid-phase synthesis method is adopted, mixing 4-hydroxybenzophenone hydrazone with o-hydroxybenzaldehyde according to the mass ratio of 4: 1-1: 4, and grinding for reaction for 1-10 hours to obtain a target product; recrystallizing with methanol, ethanol, acetonitrile, dichloromethane, chloroform, tetrahydrofuran or acetone to obtain target product crystal.
3. Use of a compound as claimed in claim 1, or a pharmaceutically acceptable salt thereof, for the manufacture of a medicament for the treatment of tumours, wherein: the tumor is lung cancer, breast cancer or liver cancer.
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Non-Patent Citations (2)
| Title |
|---|
| A colorimetric and turn-on fluorescent chemosensor for selective detection of Hg2+:theoretical studies and intracellular applications;Rimi Roy等;《RSC Adv.》;20150731;第67833-67840页 * |
| Specific Fluorescence Probes for Lipid Droplets Based on Simple AIEgens;Zhiming Wang等;《ACS Appl. Mater. Interfaces》;20160407;第10193-10200页 * |
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